程 磊,曾 濤,陳云霞,馮詩樂,蘇小麗,施 瑋
(景德鎮(zhèn)陶瓷大學(xué),江西 景德鎮(zhèn) 333403)
量子點(diǎn)敏化太陽能電池研究進(jìn)展
程 磊,曾 濤,陳云霞,馮詩樂,蘇小麗,施 瑋
(景德鎮(zhèn)陶瓷大學(xué),江西 景德鎮(zhèn) 333403)
量子點(diǎn)敏化太陽能電池因其具有低廉制備成本、較高的理論效率等優(yōu)勢,使其成為極具潛力的“第三代太陽能電池”。而電池的工作性能優(yōu)劣主要依賴于器件的光陽極、量子點(diǎn)敏化劑、電解質(zhì)及對電極的協(xié)同作用。因此,優(yōu)化該四部分成為改善電池光電轉(zhuǎn)換效率最直接途徑。本文綜述了量子點(diǎn)敏化太陽能電池中各部分最新研究動態(tài),并提出今后制備實(shí)用高效率量子點(diǎn)敏化太陽能電池可能發(fā)展方向。
太陽能電池;光陽極;量子點(diǎn)敏化劑;量子點(diǎn)敏化劑;電解液;對電極;光電轉(zhuǎn)換效率
隨著全球溫室氣體排放量的逐年加劇及石化能源類資源的有限儲量,開發(fā)利用清潔可再生能源已成全球能源界共識,也是國際學(xué)術(shù)界關(guān)注的重點(diǎn)。太陽能作為清潔可再生能源中的一種,“取之不盡,用之不竭”的特點(diǎn)使其成為社會能源發(fā)展的主要方向之一[1,2]。早在上個世紀(jì)50年代,第一塊晶硅太陽能電池的出現(xiàn),揭開了現(xiàn)代太陽能電池的研究和商用化的序幕。隨著科技不斷發(fā)展,納米技術(shù)在太陽能電池研究領(lǐng)域不斷植入催生了多種低成本、高效率的新型太陽能電池,如量子點(diǎn)敏化太陽能電池等[3,4]。
作為第三代太陽能電池代表器件之一,量子點(diǎn)敏化太陽能電池(Quantum dots-sensitized solar cells,簡稱QDSSCs)不但制備工藝簡單且使用材料成本較低[5]。此外,通過大量研究已證實(shí)無機(jī)半導(dǎo)體量子點(diǎn)(quantum dots,簡稱QDs)材料擁有特殊的理化性質(zhì),如光學(xué)帶隙的尺寸及組分依賴性、超高消光系數(shù)、較大極化動量及撞擊離化引發(fā)的“多子效應(yīng)”,以其作為光敏劑替代傳統(tǒng)染料敏化太陽能電池(Dye-sensitized solar cells,簡稱DSSCs)中的有機(jī)染料有望大幅度提高該類型太陽能電池的光電轉(zhuǎn)換效率,從而突破Shockley-Queisser所提出的理論極限值31%[6]。與DSSCs結(jié)構(gòu)類似,QDSSCs器件也由四部分構(gòu)成:光陽極、敏化劑、電解液及對電極。不同之處在于利用QDs作為敏化劑替代傳統(tǒng)的有機(jī)染料作為光敏劑,且對電極材質(zhì)選擇也隨之發(fā)生改變,其工作原理可簡要概括如下[7]:吸附在寬帶隙金屬氧化物半導(dǎo)體光陽極上的QDs受光激發(fā)而產(chǎn)生電子-空穴對,光生電子從QDs價帶進(jìn)入較高的導(dǎo)帶激發(fā)態(tài)能級后在價帶留下對應(yīng)的空穴,由于能級的匹配,QDs導(dǎo)帶中的電子可以注入到光陽極材料的導(dǎo)帶中,而相應(yīng)空穴則繼續(xù)留在QDs中,使其處于氧化狀態(tài)且?guī)д?。此時,注入電子經(jīng)由光陽極、導(dǎo)電玻璃和外電路到達(dá)對電極,在對電極的催化作用下,被氧化的QDs敏化劑通過氧化-還原電解液重新獲得電子回到基態(tài),至此完成一個工作循環(huán),如圖1所示。
然而就目前研究狀況來看,QDSSCs最高報(bào)道光電轉(zhuǎn)換效率(-9.48%[9])距離DSSCs的效率值(-13.0%[10])還有一定差距。因此,如何進(jìn)一步提高QDSSCs光電轉(zhuǎn)換效率(photoelectric conversion efficiency,簡稱PCE)使之與傳統(tǒng)DSSCs抗衡,甚至與商用硅基電池形成競爭成為科研工作者為之奮斗的目標(biāo)。如何提高QDSSCs的PCE主要依賴于其四個構(gòu)成部分的協(xié)同優(yōu)化[11]。因此,本文主要從光陽極、敏化劑、電解液及對電極這四個方面來介紹QDSSCs研究領(lǐng)域最新的研究動態(tài)。
圖1 QDSSCs器件結(jié)構(gòu)與工作原理[8]Fig.1 The general scheme of a typical QDSSCs device and its working principle
在QDSSCs中,光陽極不但提供“平臺”供QDs吸附,且還扮演著光生電子輸運(yùn)至外電路的角色。目前,在QDSSCs器件中最常見光陽極為TiO2或ZnO等寬帶隙金屬氧化物半導(dǎo)體納米顆粒組成的多孔膜,因?yàn)樵擃愋蚊驳墓怅枠O擁有超高的比表面積可供QDs足量吸附,使得器件對入射光子俘獲利用效率增大,進(jìn)而提高QDSSCs的短路電流密度輸出(Jsc)[12]。然而,光陽極表面積的增大的同時也必然增加光生電子在光陽極中的復(fù)合幾率,這直接影響QDSSCs的開路電壓及填充因子的輸出(Voc和F.F.)[13]。因此,平衡入射光子利用效率及光生電子復(fù)合問題是提高QDSSCs的光電轉(zhuǎn)換效率需解決的首要問題[14]。目前在這塊領(lǐng)域研究熱點(diǎn)是通過調(diào)控光陽極微觀形貌,借助于光陽極的“一維”高度有序化所帶來的光生電子超快輸運(yùn)特性來提高QDSSCs的PCE數(shù)值。Toyoda等提出利用TiO2納米管陣列有序形貌的光陽極所具有的高效電子傳輸能力、陷光能力及良好的電解液浸潤能力均可以改善QDSSCs的PCE數(shù)值[15]。但是比表面積過低限制了基于“一維”納米陣列結(jié)構(gòu)光陽極QDSSCs器件PCE的進(jìn)一步提高。Zhu等人提出在ZnO納米棒陣列基礎(chǔ)上輔以具有“枝杈”形貌的納米四角棒作為散光層,制成具有雙層結(jié)構(gòu)的光陽極,所對應(yīng)的QDSSCs器件的PCE較表面光滑的ZnO納米棒陣列相比大幅度提高,PCE數(shù)值可達(dá)到5.24%[16]。同樣Rao等人基利用簡單的水熱法制備了具有高比表面積的納米“枝杈”形貌的TiO2陣列形貌的,將該光陽極用于QDSSCs器件中所得到的PCE數(shù)值達(dá)到4.2%,優(yōu)于基于表面光滑的TiO2納米絲陣列光陽極的QDSSCs器件[17]。此外,在“多級結(jié)構(gòu)”光陽極研究方面,Liu等人報(bào)道了新型基于FTO透明導(dǎo)電玻璃具有“三維”TiO2納米管-枝杈狀納米棒陣列作為QDSSCs的光陽極能夠有效的提高電池的光電轉(zhuǎn)換效率,原因在于光陽極超高的比表面積及優(yōu)良的散光能力。同時光陽極中存在金紅石-銳鈦礦同質(zhì)結(jié)也有助于金紅石TiO2納米棒陣列從銳鈦礦TiO2納米管收集光生電子,從而降低了整個器件內(nèi)部的暗電流。當(dāng)光陽極的厚度僅為1 μm時,電池的光電轉(zhuǎn)換效率已經(jīng)達(dá)到1.04%,比僅用TiO2納米棒陣列為光陽極的電池高出2.7倍[18]。
2.1 量子點(diǎn)敏化劑設(shè)計(jì)
從目前研究動態(tài)來看,協(xié)同敏化、摻雜及核-殼結(jié)構(gòu)提出成為QDs敏化劑設(shè)計(jì)與合成主要熱點(diǎn)方向。Lee等人設(shè)計(jì)了“瀑布”能帶結(jié)構(gòu)CdSe/CdS QDs協(xié)同敏化QDSSCs,不斷拓寬器件光譜響應(yīng)范圍,還改善電子注入效率[19]。Kamat課題組在CdSe/ CdS QDs敏化劑中引入Mn2+離子,利其d-d軌道電子躍遷(4T1-6A1)來提高QDs中光生電子壽命,器件性能在原有基礎(chǔ)上得到改善[20]。為了保留QDs敏化劑原有特性,進(jìn)一步提升QDSSCs的PCE,Pan等人基于能帶理論設(shè)計(jì)出單分散優(yōu)良的反-I型能帶結(jié)構(gòu)CdS@CdSe核-殼QDs,并將其應(yīng)用于QDSSCs,敏化光陽極經(jīng)過后期于惰性環(huán)境熱處理去除包覆有機(jī)分子后,電池的PCE可達(dá)到5.32%[21]。最近,Jiao等人在此工作基礎(chǔ)上設(shè)計(jì)合成出單分散II-型能帶結(jié)構(gòu)ZnTe@CdSe核殼QDs敏化劑,利用ZnTe與CdSe較高導(dǎo)帶能級失配度(1.22 eV)促使光生電子在QDs敏化劑表面與TiO2界面上積累誘發(fā)的電偶極化效應(yīng)(Photo-induced dipole,簡稱PID),從而提高TiO2導(dǎo)帶中電子的準(zhǔn)費(fèi)米能級以獲得更高的開路電壓(Voc)輸出,優(yōu)化后的電池PCE可達(dá)7.17%[22]。Yang等人報(bào)道通過連續(xù)離子層吸附反應(yīng)工藝在CdSeTe量子點(diǎn)表面引入CdS薄層作為鈍化層形成能帶結(jié)構(gòu)為I型核殼結(jié)構(gòu),不僅可以減少CdSeTe量子點(diǎn)表面態(tài),還可增加其受光照后的穩(wěn)定性,通過優(yōu)化CdS鈍化層的厚度及后期光陽極的鈍化工藝實(shí)施,QDSSCs的PCE可達(dá)到9.48%[9]。
2.2 附載途徑
QDs敏化劑附載直接決定了其在光陽極中的附載量及分布的均勻性,這對QDSSCs器件的工作性能表現(xiàn)至關(guān)重要。一般來說QDs附載于光陽極的途徑大體可分為2類:(1)原位沉積技術(shù),如常用的化學(xué)浴沉積法(Chemical bath deposition,簡稱CBD)[23]和連續(xù)離子層吸附反應(yīng)法(Successive ionic layer adsorption and reaction,簡稱SILAR)[24];(2)預(yù)先合成后期沉積技術(shù)[25]。
對于原位沉積技術(shù),該類方法雖然操作簡單,但光陽極中所生成QDs尺寸分布不均勻,且結(jié)晶性較差。為了克服這些缺點(diǎn),最近Liu等人在原有的SILAR工藝基礎(chǔ)上輔以周期性循環(huán)電(potentialinduced ionic layer adsorption and reaction,簡稱PILAR),改善了CdSe QDs在TiO2多孔光陽極中附載量及分布狀態(tài),將PCE從-2.53%(SILAR)提升至-4.30%(PILAR)[26]。
對于預(yù)先合成后期沉積技術(shù),這類技術(shù)可通過前期QDs合成工藝參數(shù)精確調(diào)控QDs組分、尺寸大小及分布,并能夠通過陽離子或陰離子交換工藝實(shí)現(xiàn)QDs各種復(fù)雜的合金化和核-殼結(jié)構(gòu)[27]。早期對于預(yù)先合成的QDs敏化劑后期沉積方式是將光陽極直接浸泡于QDs敏化劑的有機(jī)溶液中讓其自行吸附,該過程屬于物理直接吸附,又稱直接沉積法(Direct adsorption,簡稱DA法)。沉積過程十分耗時,且考慮到QDs尺寸無法達(dá)到分子級別,因此QDs很難均勻修飾整個光陽極,整個光陽極的飽和覆蓋率僅為14%[28]。
預(yù)先合成出QDs還可通過自組裝的方式錨接到光陽極上并應(yīng)用到QDSSCs[25],該方法又稱為分子輔助吸附法(linker-assisted adsorption,簡稱LA法)。輔助分子(又稱為linker)一般為含有硫醇(-SH)和羧基(-COOH)官能團(tuán)的小分子,如巰基丙酸(簡稱MPA)[29]等。2009年,Robel等人將MPA分子修飾的TiO2納米顆粒薄膜光陽極浸漬于三辛基氧膦包覆的CdSe QDs甲苯溶液中,很好的將QDs敏化劑附載于光陽極上[30]。最近,Pan等人利用配體交換工藝將預(yù)先合成出的CdSe0.45Te0.55QDs表面包覆的有機(jī)配體轉(zhuǎn)換成MPA分子,并通過LA法將QDs敏化劑沉積于TiO2多孔薄膜光陽極上,2 h即可使得光陽極達(dá)到飽和吸附(覆蓋率為~34%),所得電池器件PCE可達(dá)6.36%[31]。
圖2 ZnTe/CdSe與CdTe/CdS核殼QDs的能帶結(jié)構(gòu)圖及所測QDSSCs的伏安特性圖[22]Fig.2 (a) Schematic diagram of the band gap and band offsets (Unit: eV) for the interfaces between bulk ZnTe/CdSe and CdTe/CdSe; (b) Photovoltaic performance in terms of J-V curves of Champion ZnTe/CdSe, Certified ZnTe/CdSe and Champion CdTe/CdSe QDs based solar cells[22]
2.3 表面鈍化
盡管圍繞QDSSCs展開的研究工作很多,但其PCE仍難以與傳統(tǒng)的DSSCs相提并論,原因之一在于QDs表面存在著太多的表面態(tài)(表面缺陷),會造成QDSSCs內(nèi)部的固-液界面發(fā)生逆向電子遷移[32,33]。表面態(tài)通常又被為束縛態(tài),是光生電子的復(fù)合中心,可以干擾電子從QDs注入光陽極的過程,圖3給出了QDSSCs中光生電子的4類逆向電子遷移發(fā)生復(fù)合的途徑(R1-R4),亦稱之為“背向反應(yīng)”過程[34,35]。在實(shí)際QDSSCs應(yīng)用中,通常采用某些有機(jī)分子[35]或第二相半導(dǎo)體來對QDs及光陽極表面態(tài)進(jìn)行鈍化處理,以降低QDSSCs中“背向反應(yīng)”過程發(fā)生的幾率。例如利用一層很薄的ZnS層對CdSe QDs的表面態(tài)進(jìn)行鈍化處理后,電池的Jsc輸出可以提升近一倍[14,36]。此外,還可以通過對QDs表面包覆無定形的TiO2[33]、SiO2[37]、SeO2[38]薄膜、F-離子處理[39]及致密阻擋層[40]均可對QDs、光陽極表面及FTO導(dǎo)電玻璃表面起到鈍化作用。最近,Zhao等人利用亞皮秒太赫茲光譜(sub-picosecond THz spectroscopy)手段證實(shí)無機(jī)半導(dǎo)體鈍化層可以有效的抑制QDSSCs器件中光電子參與“背向反應(yīng)”幾率,利用ZnS/SiO2雙層鈍化層可將以CdSexTe1-xQDs為敏化劑的電池的PCE提升至8.55%,且器件工作穩(wěn)定性得以改善[41]。
圖3 光生電子在QDSSCs中遷移、復(fù)合途徑示意圖。T1:量子點(diǎn)導(dǎo)帶中光生電子遷移至寬帶隙半導(dǎo)體(WBSC)光陽極導(dǎo)帶;T2:電子在光陽極中輸運(yùn)過程;R1:QDs中電子被電解液中氧化性物質(zhì)俘獲;R2:QDs內(nèi)部電子直接或通過表面態(tài)間接復(fù)合過程;R3:被電解液中氧化性物質(zhì)俘獲;R4:電子在QDs/WBSC界面復(fù)合[34]Fig.3 A scheme illustrating charge transfer, transport, and recombination processes in QDSSCs. T1: photon exited electron transfer from the CB of QDs to the CB of the WBSC; T2: electron transport via WBSC; T3: hole transfer from the VB of QDs to the electrolyte; R1: electron back injection from QDs to the electrolyte; R2: electron recombination in QDs; R3: electron back injection from WBSC to the electrolyte; R4: electron recombination at the WBSC/QDs interface. SS denotes surface states[34]
Ye等人指出電解液對光陽極良好浸潤性、高效離子遷移特性、對敏化劑還原再生能力及其較低過電位在電解液/對電極界面處引發(fā)超快電子輸運(yùn)性能是高效DSSCs或QDSSCs器件電解液設(shè)計(jì)的準(zhǔn)則[42]。此外,考慮到QDSSCs的開路電壓(Voc)是由光陽極中電子的準(zhǔn)費(fèi)米能級與電解液能斯特電位差值決定,因此通過電解液組分及添加劑的精細(xì)調(diào)控獲得較低的氧化還原電勢也是高Voc輸出保證[43]。目前根據(jù)QDSSCs器件中所涉電解液的物理形態(tài)可將其簡單的分為以下三類:
3.1 液態(tài)電解質(zhì)
雖然I-/I3-有機(jī)電解液與Pt對電極組合在傳統(tǒng)DSSCs器件中獲得不錯的光電轉(zhuǎn)換效率,然而多數(shù)無機(jī)窄帶半導(dǎo)體QDs在該電解液環(huán)境中較容易發(fā)生光腐蝕現(xiàn)象,導(dǎo)致QDSSCs器件性能下降[44]。2008年,Lee等人提出以改性的水基多硫電對(S2-/ Sn2-)作為器件電解液,通過添加KCl提高電解液離子遷移特性并輔以甲醇增加其對光陽極的浸潤性,在原有基礎(chǔ)上改善器件輸出性能[45]。須指出的是,甲醇作為一種高效的空穴俘獲劑在光陽極附近所發(fā)生氧化反應(yīng)為不可逆過程,因此電解液中添加甲醇往往會造成器件效率被過高估計(jì)及輸出性能不穩(wěn)定[46]。此后,多種基于有機(jī)溶劑改性S2-/Sn2-電解液陸續(xù)提出,如Li等人將[(CH3)4N]2S/[(CH3)4N]2Sn氧化-還原電對溶解于有機(jī)溶劑3-甲氧基丙腈中,作為CdS QDSSCs器件的電解液獲得了超高Voc輸出(1.2 V),同時F.F.也高達(dá)0.89[47]。
3.2 準(zhǔn)固態(tài)電解質(zhì)
為了克服QDSSCs器件中液體電解液中有機(jī)溶劑易揮發(fā)使得器件不易封裝且長程性能不穩(wěn)定缺點(diǎn),準(zhǔn)固態(tài)凝膠及全固態(tài)電解質(zhì)概念被相應(yīng)提出[48]。一些以聚合物“三維”多孔凝膠為基體,內(nèi)含常見氧化-還原電對,如S2-/Sn2-、I-/I3-、[Co(σ-phen)3]3+/[Co(σ-phen)3]2+等準(zhǔn)固態(tài)電解質(zhì)已在QDSSCs器件中得到應(yīng)用[49-52]。但考慮到常溫條件下準(zhǔn)固態(tài)電解質(zhì)無法像液態(tài)電解質(zhì)對整個敏化光陽極保持良好的浸潤性且離子遷移率較低,因此整個準(zhǔn)固體QDSSCs器件的輸出性能并不十分理想,目前該類型電池的PCE數(shù)值一般維持在1-4%[53-55]。
3.3 固態(tài)電解質(zhì)
全固態(tài)電解質(zhì)成功應(yīng)用于QDSSCs器件克服了涉及以上兩類電解質(zhì)器件封裝難題,成為此類器件研究的熱點(diǎn)方向之一。QDSSCs用固態(tài)電解質(zhì)一般為空穴導(dǎo)體材料,按材料屬性又可分為有機(jī)和無機(jī)兩大類。目前有機(jī)空穴導(dǎo)體主要為3,4-乙撐二氧噻吩單體聚合物(PEDOT:PSS)[56]、2,2’,7,7’-四溴-9,9’-螺二、三(4-碘苯)胺(spiro-MeOTAD)[48]、3-己基噻吩聚合物(P3HT)[57]等,直接作為QDSSCs器件固態(tài)電解質(zhì)來萃取激發(fā)態(tài)QDs中的空穴已獲得不錯的器件PCE輸出,但是有機(jī)空穴導(dǎo)體的空穴遷移率、穩(wěn)定性及制造成本又阻止其在QDSSCs器件中的進(jìn)一步實(shí)際應(yīng)用[58];無機(jī)空穴導(dǎo)體一般為CuSCN,雖然該種無機(jī)空穴導(dǎo)體具有較高的空穴遷移速率,然而在引入溶液中超快結(jié)晶性質(zhì)使得其對敏化光陽極的整體“浸潤性”不佳,影響QDSSCs器件性能輸出[59]。值得注意的是鈣鈦礦結(jié)構(gòu)無機(jī)空穴導(dǎo)體CsSnI3已經(jīng)在全固態(tài)DSSCs得到了成功的應(yīng)用,并獲得10.2%不錯的光電轉(zhuǎn)換效率[60]。然而以CsSnI3作為QDSSCs器件固態(tài)電解質(zhì)鮮有報(bào)道,其對敏化光陽極良好的“浸潤”性及空穴遷移特性有可能使全固態(tài)QDSSCs器件的輸出性能在現(xiàn)有基礎(chǔ)上大幅度提高。
早期QDSSCs器件中對電極材料的研究還是借鑒了DSSCs中的貴金屬材質(zhì)對電極,如Pt、Au。然而,多數(shù)貴金屬對QDSSCs器件常用S2-/Sn2-電解液催化活性較差,如Pt對電極表面極容易對S2-離子產(chǎn)生強(qiáng)烈的化學(xué)吸附而“中毒”導(dǎo)致其催化活性的惡化,這直接影響了QDSSCs性能輸出[19]。此外,考慮到貴金屬材料成本問題,越來越多其它類型對電極材料被開發(fā)以用于取代貴金屬材料對電極,大致可以分為以下幾類:
4.1 碳基材料
由于成本低廉,對常用S2-/Sn2-電解液有著良好且穩(wěn)定的電導(dǎo)催化性能,碳基材料作為對電極已被廣泛應(yīng)用于QDSSCS器件中,如納米結(jié)構(gòu)碳[61]、石墨烯[62]等。研究表明碳基對電極材料超大比表面積及優(yōu)良導(dǎo)電性是獲得QDSSCs良好性能輸出的保證[63]。
4.2 無機(jī)化合物半導(dǎo)體材料
目前基于無機(jī)化合物半導(dǎo)體材料的研究主要集中在多元金屬硫化物薄膜,如Cu2S[64]、CuS[65]、PbS[66]等。以該類材料作為對電極的最大優(yōu)點(diǎn)在于價格低廉、適宜規(guī)模化生產(chǎn)。此外,對電解液催化活性隨“組分”可調(diào)也是該類對電極材料一大優(yōu)勢[67]。最近,華東理工大學(xué)鐘新華教授課題組克服在黃銅片上制備的Cu2S對電極導(dǎo)致器件長時間工作不穩(wěn)定、抗機(jī)械損傷性能差等缺點(diǎn),利用電鍍法在FTO透明基底上沉積Cu膜,后期利用以甲醇為溶劑的多硫溶液對所得Cu膜處理以原位生成多孔片狀Cu2S膜,所組裝的電池表現(xiàn)出高效且穩(wěn)定的輸出性能[68]。同時該工作也為在柔性透明導(dǎo)電基底上(如PET-ITO、PEN-ITO等)制備高質(zhì)量Cu2S對電極以實(shí)現(xiàn)QDSSCs全柔性化奠定前期工作基礎(chǔ)。
4.3 聚合物材料
導(dǎo)電聚合物(Conductive polymers)由于高電導(dǎo)率、透明性及穩(wěn)定性,作為一種新型DSSCs對電極材料也受到廣泛關(guān)注,尤其是在柔性DSSCs器件中,常用的如聚苯胺(PANI)、3, 4-乙撐二氧噻吩單體聚合物(PEDOT)、聚吡咯(PPy)、聚噻吩(PT)及它們的摻雜改性體等[69-71]。2011年Yeh等人利用PT、PPy、PEDOT作為QDSSCs器件對電極材料,并比較三種導(dǎo)電聚合物對電極優(yōu)劣。研究表明PEDOT材質(zhì)對電極擁有較高孔隙率及表面粗糙度,與S2-/Sn2-電解液接觸面積在三種材質(zhì)之中最為充分,因此表現(xiàn)出不錯的催化活性。然而以此類材料為QDSSCs的對電極最大不足在于所組器件的PCE數(shù)值太低[72]。
目前QDSSCs的最高PCE已與商品非晶硅薄膜太陽能電池相當(dāng),然而距離其理論值31%仍有較大差距,電池發(fā)展還處于實(shí)驗(yàn)室研究階段。如何在成本可控范圍內(nèi)進(jìn)一步提高QDSSCs的PCE以推動其商用化進(jìn)程,可以從以下幾個方面入手:
(1)在考慮與光陽極能級匹配的前體下選擇合適材質(zhì)的敏化劑,使得電池光譜響應(yīng)范圍拓寬至近紅外區(qū)甚至更長波段,合金化QDs是該研究領(lǐng)域的發(fā)展趨勢;
(2)QDs表面引入鈍化層形成核-殼結(jié)構(gòu),在減少表面缺陷復(fù)合中心的同時利用核-殼之間所形成的特定能帶結(jié)構(gòu)(如能帶I、反能帶I及能帶II等)來改善光生電子注入效率,提高電池的開路電壓輸出;
(3)如何將QDs均勻足量的附載于光陽極,提高其飽和附載率成為獲得高Jsc及Voc輸出的前提條件。除去已報(bào)到電場所提供的外力輔助,在LA吸附量子點(diǎn)工藝中,通過高真空輔助提高QDs敏化劑附載量也是一條有益思路。
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Recent Advances of Quantum Dots-sensitized Solar Cells
CHENG Lei, ZENG Tao, CHEN Yunxia, FENG Shile, SU Xiaoli, SHI Wei
(Jingdezhen Ceramic Institute, Jingdezhen 333403, Jiangxi, China)
Quantum dots-sensitized solar cells have been regarded as one of the most potential photovoltaic candidates owing to the lower cost of fabrication as well as the higher theoretical efficiency. And their outperformance mainly depends on the involving photoanode, quantum dot sensitizers, electrolyte and counter electrode. Therefore, the collaborative optimization of the four parts mentioned above becomes the most direct way to improve the photoelectric conversion efficiency of this kind of photovoltaic device. This paper reviews the recent advances in the four parts of the quantum dots-sensitized solar cells. Finally, the possible development directions in the future for the fabrication of high-efficiency and practical quantum dots-sensitized solar cells are put forward.
solar cells; photoanode; quantum dot sensitizers; electrolyte; counter electrode; photoelectric conversion efficiency
TQ174.75
A
1000-2278(2016)06-0613-08
10.13957/j.cnki.tcxb.2016.06.005
2016-03-19。
2016-05-08。
江西省教育廳落地計(jì)劃項(xiàng)目(KJLD13075);江西省教育廳科學(xué)技術(shù)研究項(xiàng)目(GJJ150886);江西省自然科學(xué)基金(20132BAB216017;20142BAB216012);景德鎮(zhèn)市科技局計(jì)劃項(xiàng)目(2012-02-20);景德鎮(zhèn)陶瓷學(xué)院博士科研啟動項(xiàng)目(00401130129)。
曾濤(1983-),男,博士,講師。
Received date: 2016-03-19. Revised date: 2016-05-08.
Correspondent author:ZENG Tao(1983-),male, Ph.D., Lecturer.
E-mail:zengtao19830823@163.com